Naphtholactam dyestuffs

ABSTRACT

Naphtholactam dyestuffs of the formula ##STR1## wherein A represents the remaining members of an aromatic ring system and R represents hydrogen, alkyl, aralkyl, cycloalkyl, alkyl, aryl or an alkylene radical bonded to the naphthalene ring in the 2-position, as well as their preparation and their use for dyeing and printing natural and synthetic materials.

This is a division of application Ser. No. 363,989, filed May 25, 1973,now U.S. Pat. No. 3,950,347.

The subject of the present invention are naphtholactam compounds of thegeneral formula ##STR2## wherein A represents the remaining members ofan aromatic ring system and

R represents hydrogen, alkyl, aralkyl, cycloalkyl, aryl or an alkyleneradical bonded to the naphthalene ring in the 2-position,

As well as processes for their manufacture, and their use for dyeing,printing and bulk-dyeing of natural and synthetic materials, and thematerials dyed and printed with these compounds.

Possible aromatic ring systems of which the remaining members aredesignated A are both monocyclic and condensed systems which can bebuilt up of aromatic-carbocyclic and/or aromatic-heterocyclic ringsfused in any desired manner and which optionally also contain fusedpartly saturated rings. Five-membered and six-membered rings arepreferred.

As examples of such aromatic radicals there may be mentioned: theradicals of benzene, naphthalene, acenaphthene, tetralin, anthracene,phenanthrene, pyrene, pyridine, pyrimidine, pyrazole, indazole,benztriazole, benz[c,d]-indole, benzdioxane-(1,3), benzdioxane-(1,4),benzdioxole and coumarine.

The aromatic radicals A and the naphtholactam ring system can also carrysubstituents.

As examples of substituents on the naphtholactam ring system there maybe mentioned alkyl, hydroxyl, alkoxy, halogen, nitro, amino, sulpho andsulphonamide groups; by alkyl groups there are especially to beunderstood those with 1-4 C atoms such as methyl, ethyl, isopropyl andn-butyl, by alkoxy groups there are especially to be understood thosewith 1-4 C atoms such as methoxy, ethoxy, n-propoxy, n-butoxy andisopropoxy, by halogen radicals there are to be understood, in additionto fluorine, especially chlorine and bromine and by sulphonamide groupsthere are especially to be understood sulphonamide radicals substitutedby low molecular alkyl radicals such as methyl, ethyl and n-butyl.

Examples of possible substituents on aromatic rings of which theremaining members are designated A are: alkyl, alkoxy, halogen, amino,alkylamino, dialkylamino, acylamino, alkylacylamino, aryl, carboxyl,carboxylic acid ester, carboxylic acid amide and sulphonic acid amide,nitrile, sulpho and sulphinic acid groups, sulphonic acid amidines,alkylsulphonyl radicals and heterocyclic radicals.

By alkyl groups there are especially understood those with 1-4 C atomssuch as methyl, ethyl, n-propyl, isopropyl and n-butyl radicals as wellas trifluoromethyl groups.

Suitable alkoxy radicals preferably contain 1-12 C atoms and theirC-chain can also be interrupted by oxygen bonded in the manner of anether. As examples of such alkoxy radicals there may be mentioned:methoxy, carboxymethoxy, ethoxy, β-methoxyethoxy, β-ethoxy-ethoxy,β-carboxyethoxy, isopropoxy, n- or sec.-butoxy, i-amyloxy, n-octyloxyand n-dodecyloxy.

As halogen radicals there may be mentioned, in addition to fluorine,especially chlorine and bromine.

Alkylamino and dialkylamino radicals preferably contain alkyl groupswith 1-4 C atoms which can be substituted by halogen, nitrile, hydroxylor C₁ -C₄ -alkoxy or can together form a saturated heterocyclicfive-membered or six-membered ring such as morpholine, N-(C₁-C₄)-alkylpiperazine, piperidine or pyrrolidine.

Examples of alkyl and dialkylamino groups are methylamino,dimethylamino, ethylamino, diethylamino, n-butylamino, di-n-butylamino,di-β-cyanoethylamino, di-β-hydroxyethylamino, di-β-methoxyethylamino,di-β-chloroethylamino, β-bromoethylamino and γ-hydroxy-n-propylaminoradicals.

Examples of suitable acylamino groups are: alkylcarbonylamino groupswith 1-6 C atoms which can also be substituted, for example by halogenor nitrile, such as acetylamino, trifluoroacetylamino, cyanoacetylamino,propionylamino, β-chloro-propionylamino, n-butyroylamino andn-caproylamino; aralkylcarbonylamino groups, especially phenylalkylcarbonylamino groups with 1-3 C atoms in the alkyl radical which areoptionally substituted by halogen or C₁ -C₄ -alkyl, such asbenzylcarbonylamino, p-chlorobenzylcarbonylamino,p-methylbenzylcarbonylamino, p-t-butylbenzylcarbonylamino,β-phenylethylcarbonylamino and γ-phenyl-n-propylcarbonylamino;arylcarbonylamino groups such as benzoylamino and naphthoylaminoradicals which can be substituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄-alkoxy, nitrile and carboxylic acid alkyl ester with 1-4 C atoms in thealkyl radical, such as benzoylamino, p-methylbenzoylamino,p-ethoxybenzoylamino, p-cyanobenzoylamino,p-methoxycarbonylbenzoylamino, p-chlorobenzoylamino andm-bromobenzoylamino; alkylaminocarbonylamino anddialkylaminocarbonylamino radicals with 1-4 C atoms in the particularalkyl radical, such as methylamino-carbonylamino,ethylamino-carbonylamino, diethylamino-carbonylamino andn-butylaminocarbonylamino; arylaminocarbonylamino radicals such asphenylamino-carbonylamino radicals which are optionally substituted byC₁ -C₄ -alkyl, halogen or C₁ -C₄ -alkoxy, such asphenylamino-carbonylamino, p-toluylamino-carbonylamino,p-chlorophenylamino-carbonylamino andp-methoxyphenylamino-carbonylamino; alkylsulphonylamino radicals,especially those with 1-6 C atoms which can also be substituted, forexample by hydroxyl or halogen, such as methylsulphonylamino,ethylsulphonylamino, n-butylsulphonylamino,ω-hydroxy-n-butylsulphonylamino, ω-chloro-n-propylsulphonylamino andn-hexylsulphonylamino; aralkylsulphonylamino radicals such asbenzylsulphonylamino; arylsulphonylamino radicals, especiallyphenylsulphonylamino and naphthylsulphonylamino radicals which areoptionally substituted by halogen, C₁ -C₄ -alkyl and C₁ -C₄ -alkoxy,such as phenylsulphonylamino, p-toluylsulphonylamino,m-chlorosulphonylamino, p-methoxyphenylsulphonylamino and1-naphthylsulphonylamino; 1,3,5-triazinylamino and 1,3,5-triazinyl-C₁-C₃ -alkylamino, which can be substituted by halogen, C₁ -C₄ -alkoxy,phenoxy, phenyl, C₁ -C₄ -alkylmercapto, C₁ -C₄ -alkylamino, di-(C₁ -C₄-alkyl)-amino, morpholino and/or piperidino, such as2,4-dichloro-triazinyl-6-amino, 2,4-dichloro-triazinyl-6-methylamino,2,4-dichlorotriazinyl-6-ethylamino,2,4-dichloro-triazinyl-6-n-propylamino,2-di-β-hydroxyethylamino-4-chloro-triazinyl-6-amino,2-n-propylamino-4-chloro-triazinyl-6-amino, 2-morpholino- or2-piperidino-4-chloro-triazinyl-6-amino,2-phenylamino-4-chlorotriazinyl-6-methylamino,2-ethoxy-4-chloro-triazinyl- 6-amino,2-phenoxy-4-chloro-triazinyl-6-amino,2-phenyl-4-chlorotriazinyl-6-amino,2-β-hydroxyethylmercapto-4-chloro-triazinyl-6-amino,2,4-bis-diethylamino-triazinyl-6-amino and2-methoxy-4-di-n-butylamino-triazinyl-6-amino; pyrimidylamino radicals,especially those which are substituted by halogen, such as2,4-dichloropyrimidyl-6-amino, 2-fluoro-6-chloro-pyrimidyl-6-amino and2,4-difluoro-5-chloro-pyrimidyl-6-amino; and also2,3-dichloroquinoxaline-6-carbonylamino and -6-sulphonylamino radicals.Suitable alkylacylamino groups are those with 1-3 C atoms in the alkylradical, with the acylamino radical having the abovementioned meaning.

By aryl radicals there are especially to be understood phenyl andnaphthyl radicals which can in turn be substituted, especially by C₁ -C₄-alkyl radicals such as methyl, ethyl, isopropyl and t-butyl, by C₁ -C₄-alkoxy radicals such as methoxy and ethoxy, halogen radicals such aschlorine and bromine, sulpho groups, C₁ -C₄ -alkylsulphonyl radicalssuch as methylsulphonyl and ethylsulphonyl, nitrile radicals, carboxylicacid C₁ -C₄ -alkyl esters such as the methyl esters or ethyl esters, orthe carboxylic acid amide radical.

Suitable carboxylic acid ester radicals on aromatic radicals of whichthe remaining members are designated A are C₁ -C₄ -alkyl esters such asmethyl, ethyl and isobutyl esters, carboxylic acid aralkyl esters suchas the benzyl ester, and phenyl esters.

Suitable carboxylic acid amides and sulphonic acid amides as well assulphonic acid amidines contain, for example, aryl groups such asphenyl, aralkyl groups such as benzyl and phenylethyl and especiallyalkyl groups; C₁ -C₈ -alkyl groups such as methyl, cyanomethyl,carboxymethyl, ethyl, β-hydroxyethyl, β-chloroethyl, n-butyl, isobutyland n-hexyl may be singled out. Such alkyl radicals can also, togetherwith the N atom to which they are bonded, form a saturated heterocyclicfive-membered or six-membered ring such as pyrrolidine, piperidine,morpholine or N-C₁ -C₄ -alkyl-piperazine.

Preferred alkylsulphonyl radicals are methylsulphonyl and ethylsulphonylradicals.

Possible heterocyclic radicals in A are, in addition to saturatednitrogen-containing 5-membered ring and 6-membered ring heterocyclicstructures, such as pyrrolidine, piperidine, piperazine and morpholine,preferably aromatic five-membered ring heterocyclic structures such aspyrrole, pyrazole, 1,2,3-and 1,2,4-triazole, benztriazole,naphthtriazole, acenaphthtriazole, pyrazolotriazole, pyridotriazole,imidazole, benzimidazole, benzoxazole and benzthiazole.

Alkyl radicals R preferably have 1-6 C atoms and can in addition containfurther radicals, for example hydroxyl, halogen such as chlorine orbromine, alkoxy such as methoxy or ethoxy, nitrile, carboxyl, carboxylicacid ester such as methyl ester, ethyl ester or β-methoxy-ethyl ester,β-hydroxyethyl ester or β-chloroethyl ester, δ-hydroxybutyl ester,isobutyl ester and benzyl ester, carboxylic acid amides, such asdimethylamide or diethylamide, amines such as dimethylamine ordiethylamine or a saturated or aromatic five-membered or six-memberednitrogen-containing heterocyclic radical such as pyrrolidine, 1,2,4- or1,2,3-triazole, piperidine, pyridine, morpholine and benzimidazole.

As examples of such alkyl radicals R there may be mentioned: methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, isoamyl, n-pentyl,n-hexyl, β-hydroxyethyl, methoxymethyl, β-ethoxyethyl, β-methoxyethyl,β-cyanoethyl, β-chloroethyl, β-bromoethyl, ω-chloro-n-propyl,β-carboxyethyl, β-methoxycarbonylethyl, β-ethoxycarbonylethyl,β-amidocarbonylethyl, β-diethylamidocarbonylethyl,3-dimethylamino-n-propyl, β-morpholinylethyl, β-piperidinylethyl,β-1,2,3-triazolylethyl, β-pyridyl-(2)-ethyl andβ-benzimidazolyl-(2)-ethyl.

The methyl and ethyl radical are particularly preferred.

Suitable aralkyl radicals R are phenylalkyl radicals with 1-4 C atoms inthe alkyl radical, which are optionally substituted by halogen, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy. Preferred aralkyl radicals R are the benzyl,4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl and β-phenylethylradical.

As a cycloalkyl radical R, the cyclohexyl radical should especially bementioned.

Suitable phenyl radicals R are phenyl radicals optionally substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, such as, for example, phenyl,p-toluyl, 4-methoxyphenyl or 4-ethoxyphenyl or 4-chlorophenyl.

Particularly preferred radicals R are alkyl radicals and benzylradicals.

Alkylene radicals R which are cyclised with the naphthalene ring of thenaphtholactam ring system in the 2-position preferably contain 2 to 3 Catoms.

Amongst the compounds of the formula I there may be mentioned, as aparticularly valuable class, those which correspond to the formula##STR3## wherein R¹ denotes hydrogen, alkyl, aralkyl, cycloalkyl or arylor together with R² forms an alkylene radical,

R² represents hydrogen, alkyl, alkoxy, amino, nitro, halogen or sulpho,

R³ denotes alkyl or alkoxy and

B represents the remaining members of a radical of the benzene serieswhich can also be fused to a dioxole, dioxane, pyrazole or triazolering, or the remaining members of a radical of the naphthalene series,to which a pyrrolidone ring can also be fused, or of the acenaphthene,anthracene, phenanthrene or pyrene series.

In detail, the comments made above apply to the substituents andradicals mentioned.

Amongst the compounds of the formula II there should in turn beespecially singled out those which correspond to the formula ##STR4##wherein Y¹ denotes hydrogen, or a C₁ -C₅ -alkyl radical which isoptionally substituted by chlorine, hydroxyl, nitrile, carboxyl,carboxylic acid C₁ -C₄ -alkyl ester or benzyl ester, carboxylic acidamide or C₁ -C₃ -alkoxy; a benzyl radical which is optionallysubstituted by C₁ -C₂ -alkyl, chlorine, C₁ -C₂ -alkoxy or nitrile; aphenyl radical which is optionally substituted by C₁ -C₂ -alkyl,chlorine or C₁ -C₂ -alkoxy, a cyclohexyl radical or, together with Y², apropylene radical,

Y² represents hydrogen, chlorine, bromine, C₁ -C₃ -alkyl, C₁ -C₂-alkoxy, amino or sulpho,

Y³ represents hydrogen or a C₁ -C₂ -alkoxy group and

D represents the remaining members of a benzene radical which isoptionally substituted by C₁ -C₄ -alkyl, C₁ -C₁₂ -alkoxy, amino, C₁ -C₄-alkylamino, or di-(C₁ -C₄ -alkyl)amino, a C₁ -C₆ -alkylcarbonylamino or-sulphonylamino radical which is optionally substituted by a C₁ -C₃-N-alkyl radical, a phenylalkylcarbonylamino orphenylalkylsulphonylamino radical with 1-3 C atoms in the alkyl radicalwhich is optionally substituted by halogen, a C₁ -C₄ -alkyl radicaland/or C₁ -C₃ -N-alkyl radical, a benzoylamino, naphthoylamino,phenylsulphonylamino or naphthylsulphonylamino radical which isoptionally substituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,nitrile, carboxylic acid C₁ -C₄ -alkyl ester and/or a C₁ -C₃ -N-alkylradical, an alkylaminocarbonylamino or dialkylaminocarbonylamino radicalwith 1-4 C atoms in the particular alkyl radical, aphenylaminocarbonylamino radical which is optionally substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, a 1,3,5-triazinylamino or1,3,5-triazinyl-C₁ -C₃ -alkylamino radical which is substituted byhalogen, C₁ -C₄ -alkoxy, phenoxy, phenyl, C₁ -C₄ -alkylmercapto, C₁ -C₄-alkylamino, di-(C₁ -C₄ -alkyl)-amino, morpholino and/or piperidino, apyrimididylamino radical which is substituted by halogen, the2,3-dichloroquinoxaline-6-carbonylamino or -6-sulphonylamino radical,N-morpholinyl, N-piperidinyl, N-pyrrolidyl, N-pyrazolyl or N-triazolyl,it also being possible for a dioxole, dioxane or triazole ring to befused to this benzene radical, the remaining members of a naphthaleneradical which is optionally substituted by hydroxyl, C₁ -C₄ -alkoxy, C₁-C₄ -alkyl, chlorine, bromine, nitrile, carboxyl, carboxylic acid C₁ -C₃-alkyl ester, sulphonic acid, carboxylic acid amide or sulphonic acidamide optionally substituted by one or two C₁ -C₄ -alkyl radicals, anamino group optionally substituted by one or two C₁ -C₄ -alkyl radicalsor a C₂ -C₃ -alkylcarbonylamino radical, it also being possible for apyrrolidone ring to be fused to this naphthalene radical, and theremaining members of an acenaphthene, phenanthrene or pyrene radicalwhich optionally contains sulpho groups.

A particularly valuable class of compounds of the formula IIacorresponds to the formula ##STR5## wherein

Z¹ denotes hydrogen, a C₁ -C₄ -alkyl radical which is optionallysubstituted by hydroxyl, chlorine or nitrile, or a benzyl radical,

Z² represents hydrogen, methyl, ethyl or amino and E represents theremaining members of a benzene radical which can be substituted by C₁-C₂ -alkyl, C₁ -C₄ -alkoxy, methylenedioxy, amino, C₁ -C₄ -alkylamino,C₂ -C₈ -dialkylamino, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄-alkylsulfonylamino, phenylacetylamino, benzylsulphonylamino,benzoylamino, naphthoylamino, phenylsulphonylamino,naphthylsulphonylamino or dichloro-1,3,6-triazinylamino radical (saidacylamino groups are optionally substituted at the nitrogen atom by a C₁-C₂ -alkyl group; the remaining members of a naphthalene radical whichis optionally substituted by hydroxy, C₁ -C₃ -alkoxy, sulphonic acid, C₁-C₂ -alkyl, amino, C₁ -C₂ -alkylamino or C₂ -C₄ -dialkylamino; or theremaining members of an acenaphthene or phenanthrene radical or pyreneradical which is optionally substituted by one or two sulpho groups. A

A further valuable class of compounds within the scope of the generalformula I corresponds to the formula ##STR6## wherein W¹ denoteshydrogen, alkyl, aralkyl, cycloalkyl or aryl or together with W² formsan alkylene radical,

W² represents hydrogen, alkyl, alkoxy, amino, nitro, halogen or sulpho,

W³ denotes alkyl or alkoxy and

G represents the remaining members of a radical of the pyridine,pyrazole or pyrimidine series.

Amongst the compounds of the formula III there should especially besingled out those which correspond to the formula ##STR7## wherein Q¹denotes hydrogen, a C₁ -C₅ -alkyl radical which is optionallysubstituted by chlorine, hydroxyl, nitrile, carboxyl, carboxylic acid C₁-C₄ -alkyl ester or benzyl ester, carboxylic acid amide or C₁ -C₃-alkoxy, a benzyl radical which is optionally substituted by C₁ -C₂-chlorine, C₁ -C₂ -alkoxy or nitrile, a phenyl radical which isoptionally substituted by C₁ -C₂ -alkyl, chlorine or C₁ -C₂ -alkoxy, acyclohexyl radical or, together with Q², a C₃ -alkylene radical,

Q² represents hydrogen, chlorine, bromine, C₁ -C₃ -alkyl, C₁ -C₂-alkoxy, amino or sulpho,

Q³ represents hydrogen or a C₁ -C₂ -alkoxy group and

M represents the remaining members of a pyrazole radical which canoptionally be substituted by phenyl or naphthyl, which can also containC₁ -C₂ -alkyl, methoxy, halogen, carboxyl or sulpho groups, or by a C₁-C₂ -alkyl radical, or of a pyridine radical which is optionallysubstituted by amino, acetylamino, bromime, C₁ -C₂ -alkyl, carboxylicacid C₁ -C₂ -alkyl ester or carboxylic acid amide or of a pyrimidineradical which is optionally substituted by hydroxyl, C₁ -C₄ -alkyl,benzyl or phenyl radicals, it also being possible for the pyridineradical to be present as a quaternary salt.

Those compounds of the formula IIIa in which

M represents the remaining members of an α-aminopyridine radical, aswell as their quaternary salts, are preferred.

A particularly valuable class of compounds of the formula IIIacorresponds to the formula ##STR8## wherein V¹ denotes hydrogen, a C₁-C₄ -alkyl radical which is optionally substituted by hydroxyl, chlorineor nitrile, or a benzyl radical and

V² represents hydrogen, methyl, ethyl or amino,

and their quaternary salts of the formula ##STR9## wherein V¹ and V²have the meaning indicated above (formula IIIb),

U represents a C₁ -C₄ -alkyl radical which is optionally substituted byC₁ -C₂ -alkoxy, hydroxyl, nitrile, carboxyl or carboxylic acid C₁ -C₂-alkyl ester, or represents a benzyl radical which is optionallysubstituted by chlorine or methoxy and

X denotes an anion.

Suitable anions are those described, for example, in Belgian PatentSpecification 771,576.

The new naphtholactam compounds of the formula I are obtained, accordingto the invention, when o-aminoazo compounds of the formula ##STR10##wherein A and R have the abovementioned meaning are dehydrogenatedaccording to methods which are in themselves known, to give thecorresponding triazole compound.

The triazolisation reaction is appropriately carried out analogously tothe instructions of British Patent Specification 990,102, in ahydrophilic, non-oxidisable organic solvent, such as dimethylformamide,pyridine or a picoline mixture, by heating the o-aminoazo dyestuff ofthe formula V with a suitable oxidising agent, for example a copper-IIsalt such as copper-II sulphate, chloride, acetate, carbonate ornaphthenate, in the presence of water and of nitrogen bases such asammonia, diethanolamine or especially pyridine, or with an alkali metalhypochlorite, such as sodium hypochlorite.

The reaction is appropriately carried out in the temperature range of20°- 90°.

A further form of carrying out the triazolisation consists of reactingthe o-aminoazo dyestuff of the formula V, in accordance with theinstructions of German Offenlegungschrift (German PublishedSpecification) 1,803,636, with thionylaniline compounds in high-boilingsolvents such as dichlorobenzene, to give I.

The o-aminoazo compounds of the formula V are obtainable according tovarious processes. Thus, for example, o-nitro-amino compounds of theformula ##STR11## wherein A has the abovementioned meaning can bediazotised and coupled to 1-naphthylamine-8-carboxylic acid; thereafter,the lactam ring can be closed by warming with an acid and the nitrogroup can be converted to the amino group by reduction.

A particularly suitable process for the manufacture of compounds of theformula V, which is also a subject of the invention within the frameworkof the manufacture of compounds of the formula I, consists ofdiazotising 4-aminonaphtholactam compounds of the formula ##STR12##wherein R has the abovementioned meaning and coupling the resultingdiazonium compound to the o-position of an amino compound of the formula##STR13## wherein A has the abovementioned meaning.

4-Amino-N-ethyl-naphtholactam-(1,8) (VII, R = C₂ H₅) is known (GermanAuslegeschrift (German Published Specification) 1,190,126, Example 6)and is obtained by nitration of N-ethylnaphtholactam-(1,8) at 0°-20° andsubsequent reduction of the nitro compound with iron in aqueous acidsuspension. The remaining compounds of the formula VII are manufacturedanalogously (from the corresponding amino-free compounds).

The diazotisation of the compounds of the formula XI is appropriatelycarried out in a solution strongly acidified with mineral aceid, forexample sulphuric acid, at -5 to +10° C., by running in alkali metalnitrite solution and optionally stirring for several hours thereafter.

After destroying the excess nitrite and filtering, the diazonium saltsolution thus obtained is coupled at a pH value of 3-8, preferably 5-6,in the temperature range of 0°-60°, the reaction first being carried outat 5°-15° C. and the coupling then being completed by warming to40°-60°. Coupling is appropriately carried out in an aqueous oraqueous-organic medium, for example in a mixture of water and pyridine,picoline bases, dimethylformamide or a urea solution.

As examples of suitable 4-amino-naphtholactam compounds of the formulaVII there may be mentioned: 4-amino-naphtholactam-(1,8),4-amino-N-methyl-naphtholactam-(1,8),4-amino-N-ethyl-naphtholactam-(1,8),4-amino-N-n-propyl-naphtholactam-(1,8),4-amino-N-isopropyl-naphtholactam-(1,8),4-amino-N-n-butyl-naphtholactam-(1,8),4-amino-N-isobutyl-naphtholactam-(1,8),4-amino-N-isoamyl-naphtholactam-(1,8), 4-amino-N-n-hexyl-naphtholactam,4-amino-N-cyclohexyl-naphtholactam-(1,8),4-amino-N-benzyl-naphtholactam-(1,8),4-amino-N-(4'-chlorobenzyl)-naphtholactam-(1,8),4-amino-N-(4'-methyl-benzyl)-naphtholactam-(1,8),4-amino-N-β-phenylethyl-naphtholactam-(1,8),4-amino-N-phenyl-naphtholactam-(1,8),4-amino-N-(4'-methoxyphenyl)-naphtholactam-(1,8),4-amino-N-(4'-ethoxy-phenyl)-naphtholactam-(1,8),4-amino-N,2-trimethylene-naphtholactam-(1,8),4-amino-N-(4'-methylphenyl)-naphtholactam-(1,8),4-amino-N-β-cyanoethyl-naphtholactam-(1,8),4-amino-N-β-methoxyethyl-naphtholactam-(1,8),4-amino-N-β-chloroethyl-naphtholactam-(1,8),4-amino-N-β-cyanoethyl-2-methoxy-naphtholactam,4-amino-N-β-cyanoethyl-2-ethoxy-naphtholactam-(1,8),4-amino-N-methoxycarbonylmethyl-naphtholactam-(1,8),4-amino-N-β-dimethylamidocarbonylethyl-naphtholactam,4-amino-N-β-ethoxycarbonylethyl-naphtholactam,4-amino-N-β-dimethylaminoethyl-naphtholactam,4-amino-N-β-morpholinyl-ethyl-naphtholactam-(1,8),4-amino-N-β-piperidinylethyl-naphtholactam-(1,8),4-amino-N-methyl-6-methoxy-naphtholactam,4-amino-N-β-pyridyl-(2')-ethyl-naphtholactam-(1,8),4-amino-N-β-benzimidazolyl-(2')-ethyl-naphtholactam-(1,8),4-amino-N-ethyl-2-bromo-naphtholactam-(1,8),4-amino-N-ethyl-2-chloro-naphtholactam-(1,8),4-amino-N-ethyl-naphtholactam-2-sulphonic acid,4-amino-N-ethyl-2-methyl-naphtholactam-(1,8),4-amino-N,2-diethyl-naphtholactam-(1,8),4-amino-N-ethyl-7-methoxy-naphtholactam-(1,8) and4-amino-N-methyl-phenanthrenolactam-(1,10).(1-Methyl-phenanthrenolactam-(1,10) is described in Chem. Soc. 1971,3,357.)

As examples of suitable coupling components of the formula VIII theremay be mentioned: aminobenzenes such as1-amino-4-methyl-5-methoxybenzene, 1-amino-4-methyl-4-ethoxy-benzene,1-amino-4-methyl-5-n-butoxy-benzene,1-amino-4-methyl-5-isopropoxy-benzene, 1-amino-4-methyl-5-sec.butoxy-benzene, 1-amino-4-methyl-5-isoamyloxy-benzene,1-amino-4-methyl-5-n-octyloxy-benzene,1-amino-4-ethyl-5-carboxymethoxy-benzene,1-amino-4-methyl-5-n-dodecyloxy-benzene,1-amino-4-methyl-5-β-hydroxyethoxy-benzene,1-amino-4-methyl-5-β-ethoxy-ethoxy-benzene,1-amino-4-methyl-5-β-carboxyethoxy-benzene,1-amino-4-chloro-5-methoxy-benzene, 1-amino-4,5-dimethoxy-benzene,1-amino-4,5-diisopropoxy-benzene,1-amino-4,5-di-β-carboxyethoxy-benzene,1-amino-4,5-methylenedioxy-benzene, 1-amino-4,5-dimethyl-benzene,6-amino-benzdioxane-(1,3), 6-amino-benzdioxane-(1,4) and4,4'-diamino-2,2'-dimethoxy-diphenyl; diaminobenzenes such as1,3-phenylenediamine, 1,3-diamino-4-methyl-benzene,1,3-diamino-4-methoxy-benzene, 1,4-diamino-3-methoxy-benzene,1,3-diamino-4-chloro-benzene, N,N-dimethyl-1,3-phenylenediamine,N,N-diethyl-1,3-diaminobenzene, 3-acetamino-4-methyl-aniline and3-n-propionylamino-4-methyl-aniline; aminonaphthalenes such as2-aminonaphthalene, 2-amino-5-methoxynaphthalene,2-amino-6-methoxynaphthalene, 2-amino-7-methoxynaphthalene,1-amino-4-methylnaphthalene, 1-amino-4-methoxynaphthalene,1-amino-4-ethoxynaphthalene, 1-amino-4-n-propoxynaphthalene,1-amino-4-isopropoxynaphthalene, 1-amino-5-8-dichloronaphthalene,1-amino-4-diethylaminonaphthalene, 1-amino-5-methylsulphonylnaphthalene,2-amino-8-naphthol, 1-naphthylamine-4-sulphonic acid,1-naphthylamine-5-sulphonic acid, 1-naphthylamine-4,8-disulphonic acid,2-naphthylamine-1-sulphonic acid, 2-naphthylamine-6-sulphonic acid,2-naphthylamine-3,6-disulphonic acid, 1-naphthylamine-4-sulphonamide,1-naphthylamine-5-sulphonamide, 2-naphthylamine-6-sulphonamide,1-naphthylamine-4-dimethylsulphonamide,1-naphthylamine-5-diethylsulphonamide,2-naphthylamine-6-diethylsulphonamide,2-naphthylamine-7-methylsulphonamide,1-naphthylamine-4-(3'-dimethylaminopropyl)-sulphonamide,3-carboxy-2-aminonaphthalene-6-sulphonic acid,6-ethoxycarbonyl-1(2)-naphthylamine and 2-sulphomethylaminonaphthalene;aminoacenaphthenes such as 4- or 5-aminoacenaphthene,6-chloro-5-aminoacenaphthene and 6-methoxy-5-amino-acenaphthene; aminocompounds of trinuclear and polynuclear aromatic hydrocarbons, such as9-aminophenanthrene, 2-aminoanthracene and 3-aminopyrene, and thedipotassium salt of 2-aminoanthrahydroquinone-bis-sulphuric acid halfester; 5-aminopyrazoles such as 1-phenyl-3-methyl-5-aminopyrazole,1-p-chloro-phenyl-3-methyl-5-aminopyrazole,1-p-tolyl-3-methyl-5-aminopyrazole,1-(8'-sulphonaphthyl-(2'))-3-methyl-5-aminopyrazole,1-p-carboxyphenyl-3-methyl-5-aminopyrazole,1-m-sulphophenyl-methyl-5-aminopyrazole and1-cyanoethyl-3-methyl-5-aminopyrazole; aminopyridines such as2,5-diaminopyridine, 2,6-diamino-3-methylpyridine,2,6-diamino-4-methylpyridine, 2,6-diaminopyridine-4-carboxylic acidmethyl ester, 2,6-diamino-3-bromopyridine, 2,6-diamino-4-bromo-pyridineand 2,6-diamino-pyridine-4-carboxylic acid amide; aminopyrimidines suchas 4-amino-2,6-dihydroxy-pyrimidine; aminoindazoles such as 5- or6-aminoindazole; aminobenztriazoles such as2-phenyl-5-amino-benztriazole, 2-(p-cyanophenyl)-5-amino-benztriazole,2-(p-methoxyphenyl)-5-amino-benztriazole,2-phenyl-6-chloro-5-aminobenztriazole,2-phenyl-6-methyl-5-amino-benztriazole,2-phenyl-6-methoxy-5-amino-benztriazole,2-α-naphthyl-5-amino-benztriazole,5-(p-chlorophenyl)-5-amino-benztriazole and2-(p-sulphophenyl)-5-amino-benztriazole; and amino-benz[c,d]-indolessuch as 4-amino-N-ethyl-naphtholactam-(1,8),4-amino-N-methyl-naphtholactam-(1,8),4-amino-N-β-cyanoethyl-naphtholactam-(1,8) and 4-aminocoumarine.

Compounds of the formula I which in addition to the triazole nitrogenatoms shown in the general formula I contain at least one tertiaryquaternisable nitrogen atom can be converted into quaternary dyestuffsalts by reaction with quaternising agents -- within the scope of theformula I.

Examples of such tertiary groupings containing quaternisable nitrogenare dialkylamino groups or N-heterocyclic structures such as morpholine,piperidine, pyrrolidine, imidazole, benzimidazole, 1,2,3-triazole,1,2,4-triazole, thiazole or pyridine. Compounds of the formula I inwhich A represents the remaining members of a pyridine radical should besingled out as being particularly suitable for a quaternisation.

Examples of suitable quaternising agents are alkyl halides such asmethyl iodide, ethyl bromide, n-propyl bromide, i-propyl chloride, allylbromide, n-butyl bromide, isoamyl chloride, sulphuric acid esters oflower alkanols such as dimethylsulphate, diethylsulphate or dimethylpyrosulphate, aromatic sulphonic acid esters such as p-toluenesulphonicacid methyl ester, ethyl ester, β-chloroethyl ester and β-cyano-ethylester, m-chlorobenzenesulphonic acid ethyl ester and substituted alkylhalides such as β-chloropropionitrile, 3-dimethylamino-n-propylchloride, 4-hydroxybutyl bromide, phenylethyl bromide, benzyl chloride,p-chlorobenzyl chloride, p-methoxy-benzyl chloride, p-cyanobenzylchloride, 2-bromo-diethyl ether, bromoacetic acid methyl ester,β-chloropropionic acid ethyl ester, β-bromopropionic acid dimethylamide,ethylene oxide, propylene oxide or glycidyl methyl ether in glacialacetic acid or vinyl pyridine in formic acid. Dimethylsulphate anddiethylsulphate are particularly preferred.

The new naphtholactam compounds of the formula I are predominantlyyellow to red crystalline powders which dissolve in organic media,especially solvents such as alcohols, esters, amides, lower fatty acids,ethers and ketones to give an intense yellow-green to lemon-yellowfluorescence. The naphtholactam compounds containing sulpho groups, orquaternary salts, also dissolve in water.

The naphtholactam compounds of the formula I are valuable dyestuffs ordyestuff intermediate products. They are outstandingly suitable fordyeing oils and for bulk-dyeing of macromolecular organic materials suchas lacquers, films, sheets, fibres and mouldings, for example those ofcellulose esters such as cellulose21/2-acetate and triacetate, polyvinylcompounds such as polyvinyl chloride and polyvinyl acetate,polyurethanes, polystyrene, polyesters and polycarbonates, in veryclear, brilliant, predominantly luminous yellow shades. For this end useit is in particular possible to employ the compounds of the formula Iwhich are not salt-like, as well as those compounds containing sulphogroups which are in the form of salts of suitable organic cations suchas, for example, of alkylamines which confer lipid solubility or thosequaternary salts which are in the form of salts of suitable organicanions which confer lipid solubility.

These compounds can also be milled into the materials mentioned togetherwith pigment dyestuffs, especially yellow pigments, whereby asubstantial improvement in appearance is achieved.

A further preferred field of use for the naphtholactam dyestuffsaccording to the invention, of the formula I, is the dyeing and printingof natural and synthetic fibre and fabric materials. Whilst thedyestuffs containing sulpho groups are particularly suitable for dyeingpolyamide, polyurethane and wool fibres, particularly good effects andfastness properties are obtained on polyester fibres and fabrics withthe dyestuffs which are not salt-like.

Materials which are particularly suitable for dyeing with the basicdyestuffs amongst those of the formula I are flocks, fibres, filaments,tapes, woven fabrics or knitted fabrics of polyacrylonitrile or ofcopolymers of acrylonitrile with other vinyl compounds such as vinylchloride, vinylidene chloride, vinyl fluoride, vinyl acetate,vinylpyridine, vinylimidazole, vinyl alcohol, acrylic acid esters andmethacrylic acid esters and acrylic acid amides and methacrylic acidamides, and asymmetrical dicyanoethylene, or flocks, fibres, filaments,tapes, woven fabrics or knitted fabrics of acid-modified aromaticpolyesters and of acid-modified polyamide fibres. Acid-modified aromaticpolyesters are, for example, polycondensation products ofsulphoterephalic acid and ethylene glycol, that is to say polyethyleneglycol terephthalates containing sulphonic acid groups (type Dacron 64of E. I. DuPont de Nemours and Company) such as are described in BelgianPatent Specification 546,179 and U.S. Pat. No. 2,893,816.

Using the dyestuffs according to the invention, of the formula I, verybrilliant dyeings in greenish-tinged to reddish-tinged yellow shades,which fluoresce yellow-green to yellow in ultraviolet light anddaylight, are produced on the fibres and fabrics mentioned; the dyeingsare distinguished by good build-up and affinity and by good fastnessproperties such as fastness to washing, rubbing, sublimation,perspiration and flue gas and, for fluorescent dyestuffs, very goodfastness to light and heat stability. The fact that they are largelyinsensitive to changes in pH value should also be singled out.

The compounds hitherto proposed as fluorescent yellow dyestuffs do notpossess these advantageous properties to the same extent.

The dyestuffs according to the invention, of the formula I, can be usedfor dyeing and printing in accordance with customary processes, forexample in the form of aqueous solutions, dispersions or printingpastes. The dye baths and printing pastes can contain the customarydyeing auxiliary additives such as levelling agents, dispersing agentsand dyeing accelerators, for example substituted polyglycol ethers,condensation products of aromatic sulphonic acids and formaldehyde,condensation products of higher-molecular aliphatic amines and ethyleneoxide, higher-molecular alkyl sulphates and alkyl sulphonates in theform of their aqueous sodium salts or cyclohexylamine salts,condensation products of higher-molecular alcohols and ethylene oxide,cellulose sulphite waste liquor products, o-hydroxy-diphenyl,halogenated aromatic hydrocarbons and/or esters of aromatic carboxylicacids.

The dyestuffs according to the invention can also advantageously be usedfor dyeing from organic solutions, for example from solutions in whichwater-immiscible solvents such as tetrachloroethylene,trichloroethylene, 1,1,2-trichloroethane or 1,1,1-trichloropropane areused.

Basic dyestuffs of the formula I are suitable for dyeing mouldings ofpolymers or copolymers of acrylonitrile, asymmetrical dicyanoethylene,acid-modified aromatic polyesters or acid-modified synthetic polyamides,from chlorinated hydrocarbons as the dye bath, if the dyestuffs carrysubstituents which assist the solubility in chlorinated hydrocarbons,for example the tertiary butyl group, or if An⁻ is the anion of amonobasic organic acid with 4- 30 carbon atoms. Examples of such organicacids are: 2-ethylcaproic acid, lauric acid, oleic acid, linoleic acid,a mixture of aliphatic carboxylic acids with 15- 19 carbon atoms(Versatic Acid 1,519), a mixture of aliphatic carboxylic acids with 9-11 carbon atoms (Versatic Acid 911), coconut fatty acid first runnings,tetradecanoic acid, undecylenic acid, dimethylpropanoic acid,dimethylacetic acid, carboxylic acids of which the carbon chain isinterrupted by hetero-atoms, such as nonylphenoltetraethyleneglycol-ether-propionic acid, nonylphenol-diethyleneglycol-ether-propionic acid, dodecyl-tetraethyleneglycol-ether-propionic acid, 3-(nonyloxy)-propionic acid,3-(isotridecyloxy)-propionic acid, 3-(isotridecyloxy)-diethyleneglycol-ether-propionic acid, the ether-propionic acid of an alcoholmixture with 6-10 carbon atoms, nonylphenoxyacetic acid, aromaticcarboxylic acids such as tert.-butyl-benzoic acid, cycloaliphaticcarboxylic acids such as hexahydrobenzoic acid, cyclohexenecarboxylicacid, abietic acid and sulphonic acids such astetrapropylenebenzenesulphonic acid.

Basic dyestuffs of the formula (I) in which one of the acids listed hereforms the anion are preferred. If the basic dyestuffs are in the form ofsalts of the monobasic organic acids with 4- 30 carbon atoms which havebeen mentioned, concentrated solutions, of good stability, of thesedyestuffs in chlorinated hydrocarbons can be prepared, if appropriatewith addition of polar organic solvents which are completely misciblewith chlorinated hydrocarbon, such as butyrolactam, dimethylformamide,methanol, dioxane, acetonitrile, methyl ethyl ketone, nitrobenzene,dimethylsulphoxide, benzonitrile and 2-nitrochlorobenzene.

To manufacture such solutions, the methine dyestuffs according to theinvention, in the form of salts of organic acids with 4-30 carbon atoms,are stirred in, if appropriate with addition of polar organic solventswhich are completely miscible with chlorinated hydrocarbons, and ifappropriate at elevated temperature.

Basic dyestuffs of the formula (I) form light-fast pigments, which canadvantageously be employed in paper printing, with anionic precipitantssuch as alumina, tannin, phosphotungstic acids and phosphomolybdicacids.

In the examples which follow, parts are to be understood as parts byweight. The temperature data are degrees Centigrade.

EXAMPLE 1

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are suspended in 250parts by volume of water and 80 parts by volume of 36% strengthhydrochloric acid and 0.5 parts of tributyl phosphate as an anti-foamingagent are added whilst stirring. About 62 parts by volume of 30%strength by volume sodium nitrite solution is allowed to run in slowly,whilst cooling externally with ice and whilst stirring, until an excessof nitrite persists. The suspension is stirred for a further 3 hours at0° whilst maintaining an excess of nitrite, the excess nitrite isdestroyed with amidosulphonic acid, the ice-cold diazonium salt solutionis filtered and is subsequently slowly run into a solution of 27.4 partsof 1-amino-4-methyl-5-methoxy-benzene in 520 parts of water and 12 partsof 36.5% strength hydrochloric acid at about 5°-15°, and at the sametime saturated sodium acetate solution is added so as always to maintaina pH value of 5-6. After stirring for a further hour at 10°-25° thecrystalline red dyestuff is filtered off, washed with water and pressedout well.

The dyestuff, whilst still moist, is introduced into 900 parts by volumeof pyridine. 180 parts of crystalline copper sulphate and 200 parts byvolume of water are added whilst stirring and the mixture is heated tothe boil under reflux for 1 hour. It is then poured out onto 6,000 partsby volume of water. The crystalline precipitate is filtered off, washedwith water and recrystallised from 600 parts by volume of toluene, thewater being removed azeotropically and the solution subsequentlyclarified with 6 parts of Tonsil. 27 parts of the compound of theformula ##STR14## are obtained. The compound dissolves in toluene togive a strongly greenish-tinged yellow colour and a green-yellowfluorescence.

If instead of 1-amino-4-methyl-5-methoxy-benzene the equivalent amountof 6-amino-benzdioxane-(1,3) is employed, 24 parts of the compound ofthe formula ##STR15## are obtained; this compound dissolves in tolueneto give a strongly greenish-tinged yellow colour and a green-yellowfluorescence.

The following compounds are manufactured in an analogous procedure,using the appropriate starting compounds:

                                      Table                                       __________________________________________________________________________    Compounds of the formula                                                                     ##STR16##                                                      Com-                                        Colour of                         pound                                       fluorescence                       No. R        Y.sub.1                                                                          Y.sub.2   Colour of solution in toluene                                                                  in toluene                        __________________________________________________________________________    (3)  C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         strongly greenish-tinged yellow                                                                green-yellow                      (4)  NCCH.sub.2CH.sub.2                                                                     CH.sub.3                                                                          ##STR17##                                                                                "                "                               (5)  CH.sub.3 CH.sub.3                                                                          ##STR18##                                                                                "                "                               (6)  H        CH.sub.3                                                                         (CH.sub.2).sub.3CH.sub.3                                                                  "                "                               (7)                                                                                 ##STR19##                                                                             CH.sub.3                                                                         CH.sub.2COOH                                                                              "                 "                              (8)                                                                                 ##STR20##                                                                             CH.sub.3                                                                         (CH.sub.2).sub.11CH.sub.3                                                                 "                "                               (9)  C.sub.2 H.sub.5                                                                        CH.sub.3                                                                         C.sub.2 H.sub.4OC.sub.2 H.sub.5                                                           "                "                               (10) CH.sub.3 (CH.sub.2).sub.3                                                              Cl CH.sub.2CH.sub.2OH                                                                        "                "                               __________________________________________________________________________

EXAMPLE 2

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instructions of Example 1. 31 parts of4-amino-veratrol are suspended in 300 parts by volume of water anddissolved by adding 30 parts by volume of 36% strength hydrochloricacid. The solution is cooled to 10° and the diazonium salt solution isadded over the course of 20 minutes at 15°. A pH value of 5- 6 ismaintained constantly by simultaneously running in sodium acetatesolution. After stirring for a further 2 hours at 15°-20° thecrystalline precipitate is filtered off, washed with water and wellpressed out.

The dyestuff, whilst still moist, is introduced into 800 parts by volumeof pyridine. 180 parts of crystalline copper sulphate and 120 parts byvolume of water are added whilst stirring and the mixture is heated tothe boil under reflux for 1 hour and is poured out at 60° into 6,000parts of water. The crystalline precipitate is filtered off, washed withwater and dried in vacuo at 60°. 31 parts of the compound of the formula##STR21## are obtained.

The compound is purified by recrystallisation from 180 parts ofmethylglycol, subsequent hot extraction with methylcyclohexane,recrystallisation of the evaporation residue from 200 parts of tolueneand clarification with 4 parts of Tonsil. The compound dissolves intoluene to give a greenish-tinged yellow colour and green-yellowfluorescence.

If instead of 4-amino-veratrol the equivalent amount of1-amino-4,5-diisopropoxybenzene is employed, 49 parts of compound of theformula ##STR22## are obtained. The compound purified by hot extractionwith methylcyclohexane and recrystallisation from toluene also dissolvesin toluene to give a greenish-tinged yellow colour and green-yellowfluorescence.

The following compounds are manufactured analogously, using theappropriate starting compounds: ##STR23##

All three substances dissolve in dimethylformamide to give a yellowcolour and green-yellow fluorescence.

EXAMPLE 3

106 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instruction of Example 1. 115 parts of2-naphthylamine-1-sulphonic acid are dissolved in 1,500 parts by volumeof water whilst adding 500 parts by volume of saturated sodium acetatesolution and the mixture is clarified, whilst cold, with 3 parts ofactive charcoal. The diazonium salt solution is allowed to run slowlyinto this solution at 10°-15° whilst stirring, the pH being kept in therange of 4- 5 by simultaneous further addition of saturated sodiumacetate solution (a total of 3,500 parts by volume). Thereafter thereaction mixture is stirred for a further 2 hours, whilst allowing thetemperature to rise to room temperature. The crystalline red dyestuff isfiltered off, washed with water and pressed out well.

The dyestuff, whilst still moist, is introduced into 900 parts by volumeof pyridine. A solution of 300 parts of crystalline copper sulphate in200 parts by volume of water is added whilst stirring and the mixture isheated to 85°-90° over the course of 30 minutes and kept at thistemperature for 30 minutes. The crystalline precipitate is filtered offat 15°, washed with water and dried in vacuo at 30°. 62 parts of thecompound of the formula ##STR24## are obtained. After twicerecrystallising from toluene, using Tonsil, the compound is pure. Itdissolves in toluene to give a greenish-tinged yellow colour andgreen-yellow fluorescence.

The following compounds are manufactured analogously using theappropriate starting compounds:

                  Table                                                           ______________________________________                                         Compounds of the formula                                                      ##STR25##                                                                    Compound                Colour of Colour of                                   No.                     solution  fluoresecence                                       R               in benzene                                                                              in benzene                                  ______________________________________                                        (17)    CH.sub.3        greenish- green-yellow                                                        tinged                                                                        yellow                                                (18)    CH.sub.3(CH.sub.2).sub.3                                                                      "         "                                           (19)                                                                                   ##STR26##      "         "                                           (20)                                                                                   ##STR27##      "         "                                           (21)                                                                                   ##STR28##      "         "                                           (22)                                                                                   ##STR29##      "         "                                           (23)    ClCH.sub.2CH.sub.2                                                                            "         "                                           (24)    NCCH.sub.2CH.sub.2                                                                            "         "                                           (25)    HOOCCH.sub.2CH.sub.2                                                                          "         "                                           (26)                                                                                   ##STR30##      "         "                                           ______________________________________                                    

EXAMPLE 4

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instructions of Example 1. 52.6 parts of2-naphthylamine-7-sulphonic acid hydrochloride are dissolved in 1,000parts of water whilst warming and the solution is cooled to 15° C. Thediazonium salt solution is allowed to run slowly into this solution at15°-20° and at the same time saturated sodium acetate solution is addedin such a way as always to maintain a pH value of 5- 6. After stirringfor a further 2 hours at room temperature, the crystalline red dyestuffis filtered off, washed with 5% strengrh sodium chloride solution andwell pressed out.

The dyestuff, whilst still moist, is introduced into 800 parts by volumeof pyridine. 180 parts of crystalline copper sulphate and 150 parts byvolume of water are added whilst stirring, the mixture is heated to theboil under reflux for 10 minutes and the solvent is subsequently removedby distilling off in vacuo. The residue is taken up in 1,000 parts ofhot water. After cooling, the crystalline precipitate is filtered off,washed with water until the water issues colourless, twicerecrystallised, in each case from 500 parts by volume ofdimethylformamide and using 5 parts of active charcoal, washed withmethanol and dried at 70° in vacuo.

42 parts of the compound of the formula ##STR31## are obtained. Thecompound dissolves in dimethylformamide or glacial acetic acid to give ayellow colour and green-yellow fluorescence. It also gives a yellowsolution in water but with only a weak greenish-yellow fluorescence.Treatment of (27) with 2 N sodium hydroxide solution or potassiumhydroxide solution and salting out with NaCl or KCl yields thecorresponding alkali metal salts. The following compounds aremanufactured by an analogous procedure, using the appropriate startingcompounds:

                                      Table                                       __________________________________________________________________________    Compounds of the formula                                                       ##STR32##                                                                    Compound                                   Solution/fluoresence colour        No.   R          X R.sup.1                                                                              R.sup.2  R.sup.3                                                                           R.sup.4                                                                           in glacial acetic                  __________________________________________________________________________                                               acid                               28    C.sub.2 H.sub.5                                                                          H SO.sub.3 K                                                                           H        H   H   greenish-tinged                                                                       green-                                                                yellow  yellow                     29    NCCH.sub.2CH.sub.2                                                                       H H      SO.sub.3 Na                                                                            H   H   "       "                          30    CH.sub.3   Br                                                                              H      H        SO.sub.3 Na                                                                       H   "       "                          31                                                                                   ##STR33## H SO.sub.3 Na                                                                          H        H   COOH                                                                              "       "                          32    CH.sub. 3 (CH.sub.2).sub.3                                                               H SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                    H        H   H   "       "                          33                                                                                   ##STR34## H H                                                                                     ##STR35##                                                                             "   "                                      34    CH.sub.3 OCH.sub.2 CH.sub.2                                                              Cl                                                                              H                                                                                     ##STR36##                                                                             H   H   "       "                          __________________________________________________________________________

EXAMPLE 5

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotisedaccording to the instructions of Example 1. 38.6 parts of9-amino-phenanthrene are dissolved in 2,000 parts by volume of pyridineat room temperature. The diazonium salt solution is allowed to run intothis solution at room temperature. After stirring for 3 hours at20°-25°, 180 parts of crystalline copper-II sulphate and 150 parts ofwater are added and the mixture is heated to the boil under reflux for 5hours and is poured out into 6,000 parts of water whilst stirring. Thecrystalline precipitate is filtered off, washed with water and dried invacuo at 60° C. 58 parts of the compound of the formula ##STR37## areobtained. The compound is purified by hot extraction withmethylcyclohexane, evaporation of the solvent in vacuo andrecrystallisation of the evaporation residue from toluene, using Tonsil.The compound dissolves in toluene to give a yellow colour and shows agreen-yellow fluorescence.

If instead of 9-amino-phenanthrene an equivalent amount of5-amino-acenaphthene is employed, 52 parts of the compound of theformula ##STR38## are obtained. After hot extraction withmethylcyclohexane and recrystallisation from toluene, a solution of thesubstance in toluene shows a yellow colour and a green-yellowfluorescence.

The following compounds are obtained by an analogous procedure using theappropriate starting compounds:

    __________________________________________________________________________                                        Colour of solution Colour of                                                  fluorescence                                                                  in toluene                                __________________________________________________________________________    (37)                                                                               ##STR39##                      greenish-tinged yellow                                                                    green-yellow                  (38)                                                                               ##STR40##                      yellow      green-yellow                  (39)                                                                               ##STR41##                      yellow      green-yellow                  (40)                                                                               ##STR42##                      yellow      green-yellow                  (41)                                                                               ##STR43##                      greenish-tinged yellow                                                                    green-yellow                  (42)                                                                               ##STR44##                                                                __________________________________________________________________________                                        reddish-tinged yellow                                                                     green-yellow              

EXAMPLE 6

10 parts of the compound of the formula (35) Example 5) are introducedinto 40 parts of 96% strength sulphuric acid at 10°- 15° and the mixtureis stirred for a further hour at the indicated temperature. 10 parts of25% strength oleum are now added dropwise at 15° - 20° and the mixtureis stirred for some hours longer at 30° - 40° until a sample iscompletely soluble in hot water. The reaction mixture is poured out onto100 parts of ice and 100 parts of water and the crystalline precipitateis filtered off, taken up in 100 parts of water, neutralised with sodiumhydroxide solution, salted out by adding 30 parts of 10% strength sodiumchloride solution, filtered off, washed with 5% strength sodium chloridesolution and dried in vacuo at 60°. 13 parts of compounds of the formula##STR45## are obtained as a yellow-red crystalline powder whichdissolves in water to give a greenish-tinged yellow colour and agreenish-yellow fluorescence.

Analogous compounds are obtained if instead of compound (35) one of theother compounds mentioned in Example 5 is employed.

EXAMPLE 7

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instructions of Example 1. A further 42.4 parts of4-amino-N-ethyl-naphtholactam are dissolved in 750 parts of pyridinewhilst warming. The clarified diazonium salt solution is allowed to runinto this solution at room temperature. After stirring for a further 3hours, 180 parts of crystalline copper sulphate and 150 parts of waterare added and the mixture is heated to the boil under reflux for 4 hoursand is then poured out onto 6,000 parts of water. The crystallineprecipitate is filtered off, washed with water and dried in vacuo at60°. 96 parts of the compound of the formula ##STR46## are obtained andare purified by recrystallisation from chlorobenzene, clarifying withTonsil, washing with methanol and drying. In chlorobenzene, the compoundshows a yellow solution colour and a greenish-yellow fluorescence. Thefollowing compounds are manufactured by an analogous procedure using theappropriate starting compounds:

    __________________________________________________________________________                                      Solution colour                                                                        Fluorescence                       __________________________________________________________________________                                               colour                              ##STR47##                        yellow (in DMF)                                                                        green-yellow                                                                             (45)                     ##STR48##                        yellow (in DMF)                                                                        green-yellow                                                                             (46)                     ##STR49##                        greenish-tinged yellow (in                                                             green-yellow                                                                             (47)                    __________________________________________________________________________

EXAMPLE 8

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instructions of Example 1. 42 parts of2-phenyl-5-amino-benztriazole are dissolved in 700 parts by volume ofpyridine whilst warming, the solution is cooled, and the ice-coldfiltered diazonium salt solution is slowly added at room temperaturewhilst stirring. After stirring for a further hour, 180 parts ofcrystalline copper sulphate are added to the mixture and the whole isheated to the boil for 2 hours whilst stirring and is poured out onto6,000 parts of water. The crystalline precipitate is filtered off,washed with water and dried in vacuo at 60°. 63 parts of the compound ofthe formula ##STR50## are obtained and are purified by recrystallisationfrom 600 parts of dimethylformamide, washing with methanol and drying.In toluene, they show a greenish-tinged yellow solution colour andgreen-yellow fluorescence.

If instead of 4-amino-N-ethyl-naphtholactam-(1,8) an equivalent amountof 4-amino-N-n-butyl-naphtholactam is diazotised and in other respectsexactly the procedure indicated is followed, 61 parts of the compound ofthe formula ##STR51## are obtained, and are purified byrecrystallisation first from dimethylformamide and then from toluene(Tonsil) and again show a greenish-tinged yellow solution colour, andgreen-yellow fluorescence, in toluene.

If, on the other hand, instead of 2-phenyl-5-amino-benztriazole anequivalent amount of 2-(4'-methylphenyl)-5-amino-benztriazole isemployed, 67 parts of the compound of the formula ##STR52## areobtained, which are purified by twice recrystallising from toluene(clarifying with Tonsil) and possess colour and fluorescence propertiessimilar to compound (48).

If instead of 2-phenyl-5-amino-benztriazole an equivalent amount of2-(4'-chlorophenyl)-5-amino-benztriazole is employed, 62 parts of thecompound of the formula ##STR53## are obtained, and are purified byrecrystallisation firstly from toluene (clarifying with Tonsil) and thenfrom chlorobenzene. In toluene, they show a greenish-tinged yellowsolution colour and a green-yellow fluorescence colour.

If instead of 2-phenyl-5-amino-benztriazole an equivalent amount of2-(4'-methoxy-phenyl)-5-amino-benztriazole is employed, 65 parts of thecompound of the formula ##STR54## are obtained, which are purified bytwice recrystallising from toluene (clarifying with Tonsil). Theydissolve in toluene to give a greenish-tinged yellow colour andgreen-yellow fluorescence.

Further, the following compounds are obtained analogously from theappropriate starting compounds:

    __________________________________________________________________________                                           Solution colour                                                                           Fluorescence               __________________________________________________________________________     ##STR55##                             greenish-tinged yellow (toluene)                                                          green-yellow                                                                           (53)               ##STR56##                             greenish-tinged yellow (toluene)                                                          green-yellow                                                                           (54)               ##STR57##                             greenish-tinged yellow (in                                                                greenish-yellow                                                                        (55)              __________________________________________________________________________

EXAMPLE 9

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotisedaccording to the instructions of Example 1. 40 parts of1,3-diaminobenzene dihydrochloride are dissolved in 200 parts of waterand the solution is cooled to 10°. The diazonium salt solution isallowed to run into this solution over the course of 30 minutes, at10° - 20°. At the same time, saturated sodium acetate solution is addedin such a way that the pH value is constantly kept between 5 and 6.After stirring for a further 6 hours, the crystalline precipitate isfiltered off, washed with water and dried in vacuo at 50°. 56 parts ofdyestuff of the formula ##STR58## are obtained. 33 parts of thiscompound are treated with 350 parts of pyridine, 90 parts of crystallinecopper sulphate and 100 parts of water and the mixture is heated to 80°for 30 minutes whilst stirring and is then poured out onto 4,000 partsof water. The crystalline precipitate is filtered off, washed with waterand dried in vacuo at 60°. 22 parts of the compound of the formula##STR59## are obtained and are purified by hot extraction withmethylcyclohexane, evaporation and recrystallisation of the evaporationresidue from dichlorobenzene (clarifying with Tonsil). The substancedissolves in DMF to give a yellow colour, but without fluorescence. Onthe other hand it has a green-yellow fluorescence in chlorobenzene.

If instead of 1,3-diaminobenzene dihydrochloride an equivalent amount of1,3-diamino-4-methoxy-benzene monosulphate or1,4-diamino-3-methoxy-benzene monosulphate is employed, 26 and 28 partsof compound of the formula ##STR60## are respectively obtained and arepurified by twice recrystallising from dichlorobenzene (clarifying withTonsil). The substance dissolves in chlorobenzene to give a yellowcolour and green-yellow fluorescence.

If instead of 1,3-diaminobenzene dihydrochloride an equivalent amount ofN,N-dimethyl-1,3-phenylenediamine dissolved in dilute hydrochloric acidis employed, 31 parts of compound of the formula ##STR61## are obtainedanalogously, and are purified by hot extraction with methylcyclohexane,clarifying the extract with Tonsil, evaporation of the filtrate andrecrystallisation of the evaporation residue from ethanol. Inchlorobenzene, the compound shows a yellow solution colour and agreen-yellow fluorescence.

Analogous compounds are also obtained if instead of 1,3-diaminobenzenedihydrochloride equivalent amounts of N,N-diethyl-1,3-phenylenediamine,1,3-diamino-4-chlorobenzene, 1,3-diamino-4-methylbenzene,3-acetamino-4-methyl-aniline an 3-n-propionylamino-4-methyl-anilinedissolved in dilute hydrochloric acid, are employed.

EXAMPLE 10

15 parts of compound of the formula (57) are warmed with 130 parts ofacetic anhydride to 50° for 30 minutes whilst stirring, and the mixtureis then cooled. The yellow crystalline precipitate is filtered off,washed with methanol and dried in vacuo at 70°.

17 parts of compound of the formula ##STR62## are obtained. The compounddissolves in chlorobenzene to give a greenish-tinged yellow colour andgreen-yellow fluorescence. In contrast to compound (57), it alsofluoresces in dimethylformamide.

Analogous acylamino compounds are obtained if instead of compound (57)an equivalent amount of compound (58) or one of the compoundsmanufactured from 1,3-diamino-4-methylbenzene or1,3-diamino-4-chlorobenzene according to Example 9 is employed.

Analogous acylamino compounds are also obtained if compound (57) or(58), instead of being reacted with acetic anhydride, is reacted withtrifluoroacetic anhydride, β-chloropropionyl chloride, n-butyrolychloride, β-chloroethylsulphonyl chloride, β-chloroacryloyl chloride,2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid chloride, benzoylchloride, p-methoxybenzoyl chloride,p-toluoyl chloride,p-toluenesulphochloride, terephthaloyl dichloride, pheneacetyl chloride,2,3-dichloroquinoxaline-6-carboxylic acid chloride orthiophene-2-carboxylic acid chloride.

EXAMPLE 11

1.85 parts of cyanuric chloride are dissolved in 100 parts by volume ofacetone and 50 parts of comminuted ice are added whilst stirring. Asolution of 3.3 parts of the compound of the formula (57) in 160 partsby volume of acetone is allowed to run into the fine suspension thusobtained over the course of 15 minutes, whilst cooling with ice andstirring, and the hydrochloric acid liberated is neutralised by dropwiseaddition of 15% strength aqueous sodium carbonate solution. After theaddition of (57), the luminous yellow suspension is stirred for afurther 3 hours at 0° - 5° whilst keeping it neutral with sodiumcarbonate solution and is poured out into 400 parts of ice water, andthe product is filtered off and dried in vacuo. 5 parts of the compoundof the formula ##STR63## are obtained.

If the further reaction of (61) with diethylamine is desired, it isexpedient to dispense with pouring out into ice water and isolating theproduct. An approximately 50% strength aqueous solution of 1.6 parts ofdiethylamine is introduced over the course of 30 minutes at 0° - 5°whilst stirring and the resulting mixture is stirred for a further 12hours at 20° - 25°. To complete the reaction, the batch is furtherheated for 1 hour to 50° and is then cooled to 5° - 10°. The crystallineprecipitate is filtered off, treated with 10% strength sodium acetatesolution, washed with water and dried in vacuo at 60°. 5.5 parts of thecompound of the formula ##STR64## are obtained. The compound dissolvesin dimethylformamide to give a yellow colour and green-yellowfluorescence. The following compounds are obtained analogously from theappropriate starting components:

                                      Table                                       __________________________________________________________________________    Compounds of the formula                                                       ##STR65##                                                                                                                     Colour                       Com-                                             of  Colour of                pound                                            of  fluor-                                                                              Sol-               No. R         R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                           R.sup.4   R.sup.5      tion                                                                              escence                                                                             vent               __________________________________________________________________________                                                     yellow                                                                             green-                                                                             DMF                63  CH.sub.3  C.sub.2 H.sub.5                                                                   CH.sub.3                                                                          H   HOCH.sub. 2CH.sub.2                                                                     H                yellow                   64  NCCH.sub.2CH.sub.2                                                                      H   H   CH.sub.3                                                                          n-Butyl   n-Butyl      "   "     "                  65  C.sub.6 H.sub.5CH.sub.2                                                                 H   OCH.sub.3                                                                         H                                                                                            ##STR66##   "   "     "                  66  CH.sub.3(CH.sub.2).sub.3                                                                H   H   C.sub.2 H.sub.5                                                                   H         C.sub.2 H.sub.5                                                                            "   "     "                  67  (CH.sub.3).sub.2 CH                                                                     H   H   H   NCCH.sub.2CH.sub.2                                                                      NCCH.sub.2CH.sub.2                                                                         "   "     "                  68  C.sub.2 H.sub.5                                                                         H   H   H   C.sub.6 H.sub.5 CH.sub.2                                                                C.sub.6 H.sub.5 CH.sub.2                                                                   "   "     "                  69  H         H   H   H   C.sub.6 H.sub.5                                                                         CH.sub.3     "   "     "                  70  CH.sub.3  Br  H   H   C.sub.6 H.sub.11                                                                        CH.sub.3     "   "     "                  __________________________________________________________________________

EXAMPLE 12

1.85 parts of cyanuric chloride are dissolved in 100 parts by volume ofacetone and 50 parts of comminuted ice are added whilst stirring. Asolution of 3.3 parts of the compound of the formula (57) in 160 partsby volume of acetone is run into the fine suspension thus obtained overthe course of 15 minutes, whilst cooling with ice and stirring and thehydrochloric acid liberated is neutralised by dropwise addition of 15%strength aqueous sodium carbonate solution. After the addition of (57),the suspension is stirred for a further 3 hours at 0° - 5° whilstkeeping it neutral with sodium carbonate solution. Thereafter a solutionof 3.3 parts of (57) in 160 parts by volume of acetone is again added at0° - 10° and the mixture is warmed to 40° - 45° over the course of 15minutes, whilst constantly maintaining a pH value of 6 - 7 by additionof 15% strength sodium carbonate solution. The pH value is also keptconstant at 6- 7 by means of sodium carbonate solution during thesubsequently post-stirring time of 4 hours at 45° - 50°. 500 parts byvolume of water at 40° are then added and the batch is stirred for 15minutes at 40°. The crystalline precipitate is filtered off, washed withwater and dried in vacuo at 70°. 7.8 parts of the compound of theformula ##STR67## are obtained. The compound is sparingly soluble in thecustomary organic solvents. In N-methylpyrrolidone it shows a yellowsolution colour and a green-yellow fluorescence.

EXAMPLE 13

6.6 parts of the compound of the formula (57) and 10 parts of2,4-bis-diethylamino-6-chloro-1,3,5-triazine in 50 parts by volume ofdimethylformamide are heated to the boil for 8 hours whilst stirringunder reflux, and the mixture is cooled and stirred with 50 parts byvolume of alcohol. The crystalline precipitate is filtered off, washedwith alcohol and dried in vacuo at 50°. 11 parts of the compound of theformula ##STR68## are obtained. The dyestuff dissolves in chlorobenzeneto give a yellow colour and green-yellow fluorescence.

If instead of compound (57) an equivalent amount of compound (58) isemployed, 12 parts of the compound of the formula ##STR69## areobtained. The compound also dissolves in chlorobenzene to give a yellowcolour and green-yellow fluorescence.

The following compounds are manufactured analogously, using theappropriate starting materials: ##STR70##

    __________________________________________________________________________                                                 (in chlorobenzene)               Com-                                         Colour                                                                              Colour of                  pound                                        of    floures-                   No. X           Y           R.sub.1  R.sub.2                                                                           R.sub.3                                                                           solution                                                                            cence                      __________________________________________________________________________                                                 greenish-                                                                           green-                                                                  tinged                           74  N(CH.sub.3).sub.2                                                                         N(CH.sub.3).sub.2                                                                         C.sub.6 H.sub.5 CH.sub.2                                                               Cl  H   yellow                                                                              yellow                     75                                                                                             ##STR71##  (CH.sub.2).sub.3 CH.sub.3                                                              H   H   "     "                          76                                                                                 ##STR72##                                                                                 ##STR73##  CH.sub.2CH.sub.2CN                                                                     H   H   "     "                          77                                                                                 ##STR74##                                                                                 ##STR75##  H        H   C.sub.2 H.sub.5                                                                   "     "                          78  NH(C.sub.4 H.sub.9)                                                                       NHC.sub.4 H.sub.9                                                                          ##STR76##                                                                             H   H   "     "                          79                                                                                 ##STR77##                                                                                 ##STR78##  CH.sub.2CH.sub.2CH.sub.3                                                               CH.sub.3                                                                          H   "     "                          80                                                                                 ##STR79##                                                                                 ##STR80##  C.sub.2 H.sub.5                                                                        H   H   "     "                          81  NH.sub.2    NH.sub.2    H        H   CH.sub.3                                                                          "     "                          82  NHCH.sub.2CH.sub.2 OH                                                                     NHCH.sub.2CH.sub.2 OH                                                                     C.sub.2 H.sub.5                                                                        H   H   "     "                          83                                                                                 ##STR81##                                                                                 ##STR82##  C.sub.2 H.sub.5                                                                        H   H   "     "                          84                                                                                 ##STR83##  N(C.sub.2 H.sub.5).sub.2                                                                  C.sub.2 H.sub.5                                                                        H   H   "     "                          85  OCH.sub.3   OCH.sub.3   C.sub.2 H.sub.5                                                                        H   H   "     "                          86  OC.sub.6 H.sub.5                                                                          NH.sub.2    C.sub.2 H.sub.5                                                                        H   H   "     "                          87  OC.sub.2 H.sub.5                                                                          OC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                        H   H   "     "                                                                       greenish-                                                                           green-                                                                  tinged                                                                              yellow                     88  OCH.sub.2CH.sub.2OCH.sub.3                                                                OCH.sub.2CH.sub.2OCH.sub.3                                                                C.sub.2 H.sub.5                                                                        H   H   yellow                           89  N(CH.sub.2 CH.sub.2 CN).sub.2                                                             N(CH.sub.2CH.sub.2CN).sub.2                                                               C.sub.2 H.sub.5                                                                        H   H   "     "                          90  NH.sub.2    NH(CH.sub.2).sub.3 CH.sub.3                                                               C.sub.2 H.sub.5                                                                        H   H   "     "                          91  N(C.sub.2 H.sub.5)                                                                        OH          C.sub.2 H.sub.5                                                                        H   H   "     "                          __________________________________________________________________________

EXAMPLE 14

33 parts of the compound of the formula (57) are suspended in 200 partsby volume of water, 40 parts by volume of 36% strength hydrochloric acidare added whilst stirring and the mixture is diazotised with 30%strength by volume hydrochloric acid whilst cooling at 0° - 5°. Thediazonium salt solution is filtered and poured, whilst stirring, into asodium sulphite suspension which has been manufactured by neutralising60 parts by volume of 38% strength technical sodium bisulphite solutionwith sodium hydroxide solution and diluting with 50 parts of water. Themixture is stirred for 3 hours at pH 6 and room temperature and is thentreated with 60 parts by volume of 36% strength hydrochloric acid andstirred for a further 3 hours at 90°. After cooling to 20°, thecrystalline precipitate is filtered off and dried. 34 parts of thecompound of the formula ##STR84## are obtained. 13.4 parts of thiscompound are stirred with a solution of 4 parts of anhydrous sodiumacetate in 40 parts of water at 50°. A solution of 6 parts ofoximinoacetophenone in 50 parts by volume of ethanol is added at pH 5.5and the mixture is warmed, whilst stirring, for 3 hours to 75° at pH5.5- 5.2. Thereafter 100 parts of water are added and the crystallineprecipitate is filtered off at room temperature, washed with water anddried at 50° in vacuo.

14.7 parts of the α-oximinohydrazone obtained are dissolved in 25 partsby volume of dimethylformamide and 20 parts by volume of pyridine. 5parts by volume of acetic anhydride are slowly run into this solutionand the mixture is heated for 2 hours to 110° and a further 2 hours to125°, the solvent is stripped off in vacuo and the residue is dilutedwith 40 parts by volume of methanol. The crystalline precipitate isfiltered off and twice recrystallised from dimethylformamide. 7 parts ofcompound of the formula ##STR85## are obtained. The compound dissolvesin chlorobenzene to give a yellow colour and green-yellow fluorescence.The following compounds are obtained analogously using the appropriatestarting materials:

                                      Table                                       __________________________________________________________________________    Compounds of the formula                                                       ##STR86##                                                                                                  (in chlorobenzene)                              Compound                      Colour  Colour of                               No.    R       X   R.sup.1                                                                              R.sup.2                                                                           of solution                                                                           fluorescence                            __________________________________________________________________________    94     CH.sub.3                                                                              C.sub.2 H.sub.5                                                                   C.sub.6 H.sub.5                                                                      C.sub.2 H.sub.5                                                                   yellow green-yellow                             95     NCCH.sub.2CH.sub.2                                                                    H   COOC.sub.2 H.sub.5                                                                   CH.sub.3                                                                           "      "                                       96     C.sub.6 H.sub.5 CH.sub.2                                                              H   C.sub.2 H.sub.5                                                                      CH.sub.3                                                                           "      "                                       97     (CH.sub.3).sub.2 CH                                                                   H                                                                                  ##STR87##                                                                           C.sub.2 H.sub.5                                                                    "      "                                       __________________________________________________________________________

If 7.6 parts of the compound of the formula (91) are condensed with 2.4parts of 1,1-dimethoxy-acetone for 2 hours in boiling n-propanol, 7parts of the compound of the formula ##STR88## are obtained. It shows ayellow solution colour and green-yellow fluorescence colour inchlorobenzene.

EXAMPLE 15

42.4 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instructions of Example 1. 34.6 parts of1-phenyl-3-methyl-5-amino-pyrazole are dissolved in 740 parts of waterwhilst adding 60 parts by volume of 36% strength hydrochloric acid andwarming. The resulting solution is cooled to 15° and the ice-cold,filtered diazonium salt solution is then added at 15°- 20° over thecourse of 30 minutes. At the same time, saturated sodium acetatesolution is added dropwise in such a way as constantly to maintain a pHvalue of 5- 6. After stirring for 2 hours at room temperature, thered-yellow crystalline precipitate is filtered off, washed with waterand firmly pressed out.

The dyestuff, whilst still moist, is taken up in 750 parts by volume ofpyridine, 180 parts of crystalline copper sulphate and 150 parts ofwater are added and the mixture is heated for 30 minutes to the boilunder reflux and poured out onto 6,000 parts of water. The crystallineprecipitate is filtered off, washed with water and dried in vacuo at70°.

51 parts of the compound of the formula ##STR89## are obtained and arepurified by recrystallisation from 600 parts of toluene (clarifying with8 parts of Tonsil and washing with methanol). The solution colour intoluene is yellow and the fluorescence colour is green-yellow.

If instead of 1-phenyl-3-methyl-5-amino-pyrazole an equivalent amount of1-(8'-sulphonaphthyl-(2')-3-methyl-5-amino-pyrazole dissolved in 1,000parts of water is employed, with addition of sodium hydroxide solutionand sodium acetate solution (pH 6), recrystallisation from 1,000 partsof glacial acetic acid, washing with acetonitrile and drying yields 31parts of the compound of the formula ##STR90## This dissolves in wateror glacial acetic acid to give a yellow colour and greenish-yellowfluorescence.

Analogously to what has been indicated for compound (99), the use ofequivalent amounts of the appropriate starting compounds yields thefollowing compounds:

    __________________________________________________________________________                                      Solution                                                                            Fluor-                                                                  colour                                                                              escence                                                                 (toluene)                                                                           (toluene)                             __________________________________________________________________________    (101)                                                                              ##STR91##                    greenish- tinged yellow                                                             green- yellow                         (102)                                                                              ##STR92##                    "     "                                     (103)                                                                              ##STR93##                    "     "                                     (104)                                                                              ##STR94##                     "    "                                     __________________________________________________________________________

example 16

36.8 parts of 4-amino-naphtholactam-(1,8) are suspended in 250 parts byvolume of water and 80 parts by volume of 36% strength hydrochloric acidare added whilst stirring. About 62 parts by volume of 30% strength byvolume sodium nitrite solution are slowly allowed to run in under thesurface at 0°, whilst cooling with ice, until an excess of nitritepersists. The mixture is stirred for a further 15 minutes at 0°, theexcess nitrate is destroyed with amidosulphonic acid and the ice-colddiazonium salt solution is filtered and is subsequently run into asolution of 35 parts of 1-phenyl-3-methyl-5-amino-pyrazole in 1,000parts of pyridine over the course of 15 minutes. After stirring for afurther 2 hours at room temperature, 180 parts of crystalline coppersulphate are added and the mixture is heated to 80° - 85° for 2 hourswhilst stirring and is then cooled to 20°. The crystalline precipitateis filtered off, washed with water until the water issues colourless anddried in vacuo at 70°. 65 parts of compound of the formula ##STR95## areobtained. The substance is purified by recrystallisation, first from1,400 parts by volume of dimethylformamide and then from 1,000 parts byvolume of o-dichlorobenzene. It dissolves in dimethylformamide to give agreenish-tinged yellow colour and green-yellow fluorescence.

Analogous compounds are obtained if instead of1-phenyl-3-methyl-5-amino-pyrazole an equivalent amount of one of thefollowing substances is employed:1-(p-chlorophenyl)-3-methyl-5-amino-pyrazole,1-p-tolyl-3-methyl-5-amino-pyrazole,1-p-carboxyphenyl-3-methyl-5-amino-pyrazole,1-cyanoethyl-3-methyl-5-amino-pyrazole and1,3-diphenyl-5-amino-pyrazole.

3 parts of the compound of the formula (105), 30 parts of acrylonitrileand 2 parts of triethylenediamine are heated for 20 hours to the boilunder reflux, whilst stirring. After cooling, the crystallineprecipitate is filtered off, washed with methanol and dried in vacuo at50°. 3.5 parts of the compound of the formula ##STR96## are obtained.The compound is purified by recrystallisation from dimethylformamide andthen shows a greenish-yellow solution colour and green-yellowfluorescence in dimethylformamide.

EXAMPLE 17

7.3 parts of the compound of the formula (105) are suspended in 70 partsby volume of dimethylformamide. 1.15 parts of powdered potassiumhydroxide are added, whilst excluding water, whereupon the suspensionassumes a luminous red colour. Thereafter 3 parts of dimethyl sulphateare added dropwise over the course of 10 minutes whilst stirring at40° - 45° and cooling, whereupon the red colouration changes to yellow.After stirring for a further 10 minutes, the addition of KOH and ofdimethyl sulphate is repeated. The mixture is then diluted with 200parts of water. The crystalline precipitate is filtered off, washed withwater and dried. 8 parts of the compound of the formula ##STR97## areobtained. This dissolves in dimethylformamide to give a greenish-tingedyellow colour and yellow-green fluorescence.

The reaction of compound (105) with the alkylating agents listed in thetable which follows is carried out analogously:

                                      Table                                       __________________________________________________________________________                 Reaction                                                                             Compound                                                                            Colour of solution                                                                       Colour of fluorescene                    Alkylating agent                                                                           temperature                                                                          No.    (in DMF)                                           __________________________________________________________________________    Diethyl sulphate                                                                           40-50°                                                                         (99) greenish-tinged                                                                          green-yellow                                                       yellow                                              Isopropyl bromide                                                                          60°                                                                           (108) "          "                                        n-Butyl bromide                                                                            60°                                                                           (109) "          "                                        Benzyl chloride                                                                            50-60°                                                                        (110) "          "                                        p-Chlorobenzyl chloride                                                                    60°                                                                           (111) "          "                                        p-Methoxybenzyl chloride                                                                   60°                                                                           (112) "          "                                        p-Methylbenzyl chloride                                                                    60°                                                                           (113) "          "                                        Isoamyl bromide                                                                            60°                                                                           (114) "          "                                        __________________________________________________________________________

To convert into the β-hydroxyethyl compound, 18.3 parts of the compound(105) are dissolved in 120 parts of dimethylformamide, 0.5 parts ofpowdered potassium hydroxide is added and about 2.5 parts of ethyleneoxide are injected in an autoclave at 120°. After 4 hours the mixture iscooled and diluted with water. The crystalline precipitate is filteredoff, washed with water and recrystallised from propanol. 16 parts of thecompound of the formula ##STR98## are obtained. This dissolves indimethylformamide to give a yellow colour and green-yellow fluorescence.The reaction with propylene oxide (instead of ethylene oxide) is carriedout analogously.

EXAMPLE 18

63.6 parts of 4-amino-N-ethyl-naphtholactam-(1,8) are diazotised inaccordance with the instructions of Example 1. 32.7 parts of2,6-diamino-pyridine are dissolved in 500 parts by volume of glacialacetic acid and 1,500 parts of water and 60 parts by volume of 36%strength hydrochloric acid are added. The ice-cold diazonium saltsolution is allowed to run into this solution over the course of 15minutes. A pH value of about 5 is maintained by simultaneously runningin a saturated sodium acetate solution. The mixture is stirred for afurther 2 hours. The crystalline red coupling dyestuff is filtered offand dried in vacuo at 60°. 55 parts of compound of the formula ##STR99##are obtained as a red crystal powder. This is suspended in 350 parts ofpyridine, mixed with 162 parts of crystalline copper sulphate and 100parts by volume of water and heated to 90° - 95° for 30 minutes. Aftercooling, the crystalline precipitate is filtered off, washed with waterand dried in vacuo at 70°. 35 parts of compound of the formula##STR100## are obtained. The compound is purified by recrystallisationfrom o-dichlorobenzene (clarifying with Tonsil). The substance dissolvesin toluene to give a yellow colour and green-yellow fluorescence. Ifinstead of 4-amino-N-ethylnaphtholactam-(1,8) the equivalent amount of4-amino-naphtholactam-(1,8) is employed (the diazotisation instructionis given in Example 16), 44 parts of the compound of the formula##STR101## are obtained. This dissolves in dimethylformamide to give ayellow colour and green-yellow fluorescence. Analogous compounds areobtained if instead of 2,6-diamino-pyridine equivalent amounts of thefollowing compounds are employed: 2,6-diamino-3-bromo-pyridine,2,6-diamino-4-bromo-pyridine, 2,6-diamino-3-methyl-pyridine,2,6-diamino-4-methyl-pyridine, 2,6-diamino-pyridine-4-carboxylic acidmethyl ester, 2,6-diamino-pyridine-4-carboxylic acid and4-amino-2,6-dihydroxypyrimidine.

The following compounds are also obtained in an analogous manner, usingthe appropriate starting materials:

    __________________________________________________________________________    Compounds of the formula                                                       ##STR102##                                                                                                 Colour of solution Colour of fluorescence       Compound No.                                                                          R          R.sup.1    in toluene                                      __________________________________________________________________________    (119)   CH.sub.3   C.sub.2 H.sub.5                                                                          yellow     green-yellow                         (120)   R + R.sup.1 =                                                                            CH.sub.2CH.sub.2CH.sub.2                                                                 "          "                                    (121)   HOCH.sub.2CH.sub.2                                                                       H          "          "                                    (122)   NCCH.sub.2CH.sub.2                                                                       Br         "          "                                    (123)                                                                                  ##STR103##                                                                              H          "          "                                    (124)                                                                                  ##STR104##                                                                              CH.sub.3 O "          "                                    (125)                                                                                  ##STR105##                                                                              H          "          "                                    (126)                                                                                  ##STR106##                                                                              H          "          "                                    (127)   CH.sub.3(CH.sub.2).sub.3                                                                 H          "          "                                    (128)                                                                                  ##STR107##                                                                              Cl         "          "                                    (129)   HOOCCH.sub.2CH.sub.2                                                                     H          "          "                                    (130)   CH.sub.3 OOCCH.sub.2                                                                     H          "          "                                    __________________________________________________________________________

EXAMPLE 19

1.4 parts of the compound of the formula (117) and 15 parts by volume ofacetic anhydride are briefly heated to the boil, diluted with 3 parts byvolume of acetone and cooled. The crystalline precipitate is filteredoff, washed with acetone and dried in vacuo at 70°. 1.3 parts of thecompound of the formula ##STR108## (mixed melting point with (117) showsa strong depression) are obtained. (131) dissolves in toluene to give ayellow colour and green-yellow fluorescence. Analogous acylaminocompounds are obtained if (117) or one of the analogous compoundsindicated in Example 18 is reacted with one of the following acylatingagents instead of acetic anhydride: trifluoroacetic anhydride,n-butyroyl chloride, β-chloropropionyl chloride, β-chloroethylsulphonylchloride, 2,2,3,3-tetrafluorocyclobutane-1-carboxylic acid chloride,β-chloroacryloyl chloride, benzoyl chloride, m-chlorobenzoyl chloride,p-toluyl chloride, p-methoxybenzoyl chloride, thiophene-2-carboxylicacid chloride, p-toluenesulphochloride and phenacetyl chloride.

EXAMPLE 20

16.5 parts of the compound of the formula (117) in 200 parts ofanhydrous chlorobenzene are treated with 7 parts of dimethyl sulphate at70° whilst stirring. The mixture is heated to 80° - 85° for 5 hours,whereupon (117) dissolves and a yellow crystalline precipitate separatesout. After cooling, this is filtered off, washed with toluene and driedin vacuo at 70°. 22 parts of the compound of the formula ##STR109## areobtained. This dissolves in water, alcohol or dimethylformamide to givea yellow colour and green-yellow fluorescence. In alcohol ordimethylformamide, the fluorescence is stronger than in water.

Analogous compounds are obtained if instead of compound (117) equivalentamounts of one of the remaining compounds indicated in Example 18 areemployed. Analogous compounds are also obtained if instead of dimethylsulphate an equivalent amount of one of the quaternising agentsindicated in the table below are employed:

                                      Table                                       __________________________________________________________________________                                   Colour of                                                                           Colour of                                                   Reaction                                                                             compound                                                                           solution                                                                            fluorescence                             Quaternising agent temperature                                                                          No.  in DMF                                         __________________________________________________________________________    Diethyl sulphate    85°                                                                          (133)                                                                              yellow                                                                              green-yellow                             p-Toluenesulphonic acid methyl ester                                                             110°                                                                          (134)                                                                              "     "                                        Benzyl chloride    120-130°                                                                      (135)                                                                              "     "                                        Ethylene oxide in glacial acetic                                                                  20-30°                                                                       (136)                                                                              "     "                                        acid                                                                          Propylene oxide in glacial acetic                                                                 20-30°                                                                       (137)                                                                              "     "                                        acid                                                                          n-Butyl bromide    140°                                                                          (138)                                                                              "     "                                                           (autoclave)                                                Allyl bromide      130°                                                                          (139)                                                                              "     "                                                           (autoclave)                                                __________________________________________________________________________

The following compounds are manufactured analogously using theappropriate starting compounds: ##STR110##

    __________________________________________________________________________    Com-                                                    Colour of             pound                                             Colour                                                                              fluorescence          No. R.sup.1   R.sup.2  R.sup.3     R.sup.4                                                                         R.sup.5                                                                             X      solution                                                                            in                    __________________________________________________________________________                                                            DMF                                                                           green-                140 H         H        CH.sub.3    H H     CH.sub.3 OSO.sub.3.sup.-                                                             yellow                                                                              yellow                141 NCCH.sub.2CH.sub.2                                                                      C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                           H H     C.sub.2 H.sub.5 OSO.sub.3.sup.-                                               1      "     "                     142                                                                                         CH.sub.3 O                                                                              ##STR111## H H     Cl.sup.-                                                                             "     "                     143                                                                                ##STR112##                                                                             H        CH.sub.3 OCH.sub.2CH.sub.2                                                                H H     Br.sup.-                                                                             "     "                     144 CH.sub.3 (CH.sub.2).sub.3                                                               H        HOOCCH.sub.2CH.sub.2                                                                      H H     Cl.sup.-                                                                             "     "                     145 CH.sub.3  Br       C.sub.2 H.sub.5 OCOCH.sub.2CH.sub.2                                                       H H     CH.sub.3COO.sup.-                                                                    "     "                     146                                                                                ##STR113##                                                                             Cl                                                                                      ##STR114## H COOC.sub.2 H.sub.5                                                                  Cl.sup.-                                                                             "     "                     147 HOCH.sub.2CH.sub.2                                                                      H        HOCH.sub.2CH.sub.2                                                                        Br                                                                              H     CH.sub.3 COO.sup.-                                                                   "     "                     148 R.sup.1+ R.sup.2=                                                                       CH.sub.2CH.sub.2CH.sub.2                                                               CH.sub.3(CH.sub.2).sub.3                                                                  H H     Br.sup.-                                                                             "     "                     149                                                                                ##STR115##                                                                             H        CH.sub.3    H H     Cl.sup.-                                                                             "     "                     150                                                                                ##STR116##                                                                             H                                                                                       ##STR117## H Br    Cl.sup.-                                                                             "     "                     __________________________________________________________________________

EXAMPLE 21

3.7 parts of the compound of the formula (105) are suspended in 25 partsby volume of glacial acetic acid. 1.6 parts by volume of 98% strengthnitric acid are added dropwise at 5°- 10° whilst cooling and stirring.The mixture is stirred for a further 3 hours at 20° and the crystallineprecipitate is filtered off at room temperature, washed with water untilneutral and dried at 50° in vacuo. 4.5 parts of the compound of theformula ##STR118## are obtained. The compound is purified byrecrystallisation from 90 parts by volume of dimethylformamide. Thesubstance dissolves in dimethylformamide to give a yellow colour andweak green-yellow fluorescence.

The reduction to the amino compound is carried out in dioxane with Raneynickel at 40° and 40 atmospheres gauge H₂ pressure. In this way, thecompound of the formula ##STR119## is obtained which dissolves indimethylformamide to give a yellow colour and shows a stronggreen-yellow fluorescence.

If instead of compound (105) an equivalent amount of compound (52) isemployed 3.0 parts of the compound of the formula ##STR120## areobtained analogously after recrystallisation from 90 parts by volume ofdimethylformamide. Reduction of (153) in dioxane with Raney nickel at40°/40 atmospheres gauge H₂ yields the compound of the formula##STR121## This dissolves in DMF to give a reddish-tinged yellow colourand reddish-tinged yellow fluorescence.

If instead of compound (105) an equivalent amount of compound (16) and(118) is employed, nitro compounds and amino compounds with similarvaluable dyestuff properties to (151) - (154) are obtained analogously.

Warming (154) with acetic anhydride yields the corresponding acetylaminocompound.

EXAMPLE 22

An approximately 1% strength dyeing wih dyestuff (11) on polyethyleneterephthalate fabric was produced as follows:

The fabric is introduced, at 50° and using a liquor ratio of 1:40, intoa dye bath which contains the finely divided dyestuff, 2 g/l of aconventional anionic dispersing agent, 5 g/l of o-cresotic acid methylester and 1 g/l of NaH₂ PO₄ and is adjusted to pH 4.5 - 5 with aceticacid. The temperature is raised to 80° - 85° over the course of 15- 20minutes and the bath is left in this temperature range for a further 20minutes. Thereafter the liquor is gradually brought to the boil. After aboiling time of 1- 11/2 hours, the dyeing process is complete.

After rinsing and drying, brilliant very strongly greenish-tinged yellowdyeings having excellent fastness properties are obtained.

Brilliant, greenish-tinged dyeings are also obtained if instead ofcompound (11) one of the following dyestuffs is employed: (1) to (10),(12) to (25), (32) to (42), (44), (47), (52) to (54), (59), (93) to(99), (101 to (115) and (117) to (131).

EXAMPLE 23

An approximately 1.3% strength dyeing with dyestuff (44) on polyamide-6fabrics was produced as follows:

The fabric is introduced at 40° and using a liquor ratio of 1:40 to1:30, into a dye bath which contains 1 g/l of a conventional anionicdispersing agent and the finely divided dyestuff. The liquor temperatureis raised to 98° (boiling point) over the course of 40- 60 minutes andthe bath is left at this temperature for about 60 minutes longer.Thereafter the fabric is rinsed and dried.

Greenish-tinged yellow dyeings with good fastness properties areobtained.

EXAMPLE 24

Polyethylene terephthalate fabric is impregnated on a padder at 40° withan aqueous liquor which contains, per liter, 10 g of finely dispersedyestuff of the formula (35), 7.5 g of sodium alginate, 20 g oftriethanolamine and 20 g of octylphenyl-polyglycol-ether. The fabric issqueezed to a liquor content of about 100% and is dried at 100° andsubsequently fixed for 30 seconds at 200° - 210°. After rinsing anddrying, a brilliant, greenish-tinged yellow dyeing having very goodfastness properties is obtained.

EXAMPLE 25

A fabric of polyethylene terephthalate is impregnated at roomtemperature with a clear padding liquor which contains 5.5 parts ofdyestuff of the formula (36) in 994.5 parts of tetrachloroethylene.After squeezing out to a weight increase of 60%, the fabric is dried forone minute at 80°. Thereafter the dyestuff is fixed for 45 seconds at220°. The fabric is washed for 20 seconds in cold tetrachloroethylene.

After drying, a brilliant, greenish-tinged yellow dyeing having verygood fastness properties is obtained.

EXAMPLE 26

30 parts by weight of the disperse dyestuff of Example 21 are dissolvedin a mixture of 50 parts by weight of thiodiglycol, 20 parts by weightof printing oil and 160 parts by volume of water. The solution isdiluted with 200 parts of water and thickened with 400 parts of crystalgum, and a printable paste is produced by adding a further 60 to 100parts of water. Polyethylene terephthalate fabrics are printed with thispaste in the usual manner and are subsequently steamed for 20 minutes ina steamer at 103° - 105°. After soaping, rinsing with water and drying,a brilliant greenish-tinged yellow colour print is obtained, which isdistinguished by good fastness to washing, rubbing, light andsublimation.

EXAMPLE 27 1.5 parts of dyestuff of the formula (27) are dissolved in300 parts of hot water, 50 parts by volume of 10% strength ammoniumacetate solution are added and the mixture is diluted with water to aliquor weight of 5,000 parts. Thereafter, 100 parts ofpoly-ε-caprolactam fabric are introduced into the dye bath at 50°, andthe bath is heated to 100° over the course of 15 minutes. The dye bathis kept at this temperature for 1 hour but after 30 minutes 3 g ofacetic acid are added. After rinsing and drying, a brilliant,greenish-tinged yellow dyeing having very good fastness properties isobtained.

Dyeings of similarly high brilliance and fastness are obtained ifinstead of the dyestuff of the formula (27) one of the followingdyestuffs is employed: (28) to (31), (43), (45), (55), (100) and (103).

EXAMPLE 28

1 part of dyestuff of the formula (27) is dissolved in 200 parts of hotwater and the solution is diluted with water to a liquor weight of 5,000parts. Thereafter 100 parts of wool fibres are introduced into the dyebath at 40°, 3 parts of acetic acid are added, the bath is heated to theboil over the course of 15 minutes and dyeing is carried out for 1 hourat the boil, with 2 parts of formic acid being added after 30 minutes.After rinsing and drying, a brilliant greenish-tinged yellow dyeinghaving good fastness properties is obtained.

EXAMPLE 29

Polyacrylonitrile fibres are introduced, using a liquor ratio of 1:40,into an aqueous bath at 40°, which contains, per liter, 0.75 g of 30%strength acetic acid, 0.38 g of sodium acetate and 0.1 g of the dyestuffof the formula (132). The dye bath is heated to the boil over the courseof 30 minutes and is kept at this temperature for 45 minutes. Afterrinsing and drying, a greenish-tinged yellow dyeing of high brillianceand excellent fastness properties is obtained.

Dyeings of a similarly high quality are obtained if instead of thedyestuff of the formula (132) one of the other dyestuffs listed inExample 20 is employed.

EXAMPLE 30

A polyacrylonitrile fabric is printed with a printing paste which hasbeen manufactured in the following manner: 30 parts of the dyestuff ofthe formula (132), 50 parts of thiodiethylene glycol, 30 parts ofcyclohexanol and 30 parts of 30% strength acetic acid are covered with330 parts of hot water and the resulting solution is added to 500 partsof crystal gum (as the thickener). Finally, 30 parts by weight of zincnitrate solution are also added.

The resulting print is dried, steamed for 30 minutes and subsequentlyrinsed. A brilliant, greenish-tinged yellow print of excellent fastnessproperties is obtained.

EXAMPLE 31

Acid-modified polyethylene terephthalate fibers are introduced, using aliquor ratio of 1:40, into an aqueous bath at 20° which contains, perliter, 5 g of sodium sulphate, 1 g of oleyl polyglycol ether (50 mols ofethylene oxide) and 0.15 g of the dyestuff of the formula (132) andwhich has been adjusted to pH 4- 5 with acetic acid. The dye bath isheated to the boil over the course of 30 minutes and kept at the boilfor 60 minutes. Thereafter the fibers are rinsed and dried. A brilliant,yellow dyeing having very good fastness properties is obtained.

EXAMPLE 32

Acid-modified synthetic polyamide fibers are introduced, using a liquorratio of 1:40, into an aqueous bath at 40° which contains, per liter, 10g of sodium acetate, 1 to 5 g of oleyl polyglycol ether (50 mols ofethylene oxide) and 0.15 g of the dyestuff of the formula (132) and hasbeen adjusted to pH 4- 5 with acetic acid. The dye bath is heated to theboil over the course of 30 minutes and is kept at the boil for 60minutes. Thereafter the fibers are rinsed and dried. A brilliant,greenish-tinged yellow dyeing with good fastness properties is obtained.

EXAMPLE 33

Polyacrylonitrile fibers are introduced, using a liquor ratio of 1:10,into a perchloroethylene bath which contains, per liter, 1 g of oleicacid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcoholwith 20 mols of ethylene oxide, 8 g of water, 1 g of glacial acetic acidand 1 g of the dyestuff of the formula (132). The dye bath is heated to100° for 60 minutes with the dyeing apparatus closed and the liquorbeing agitated vigorously. Thereafter, the fibers are rinsed inperchloroethylene and dried in a stream of air. A very clear,greenish-tinged yellow dyeing having very good fastness properties isobtained.

EXAMPLE 34

A stock solution is prepared from 15 parts by weight of dyestuff of theformula (132), 15 parts by weight of polyacrylonitrile and 70 parts byweight of dimethylformamide, and this solution is added to a customarypolyacrylonitrile spinning solution, the mixture being spun in a knownmanner. A clear, greenish-tinged yellow dyeing having good fastnessproperties is obtained.

EXAMPLE 35

0.3 of the compound (38) are mixed with 100 parts of polystyrene. Themixture is kneaded at 180° - 200° C. in an extruder to give ahomogeneously coloured mass. This is extruded through a perforatedplate. The resulting coloured polystyrene ribbons are cooled and thengranulated in a beater mill (particle diameter about 2- 4 mm). Thegranules thus obtained are converted into mouldings in an injectionmoulding machine at 220° - 300°. Transparent, fluorescent mouldings areobtained, the colourations of which have very good light fastness andmigration resistance.

EXAMPLE 36

100 parts by weight of unplasticised polyvinyl chloride, in the form ofa suspension polymer, are plastically softened on a two-roll mixing millat a roll temperature of 170° C. and using a friction of 1:1.2.Thereafter, 0.5 part by weight of titanium dioxide and 0.8 part byweight of the compound (35) are added, the mixture is milled for 10minutes, the polyvinyl chloride mass is charged onto a calender whichcan be heated, and 1 mm thick sheets are drawn off at 170° C.Yellow-coloured sheets of excellent fastness to migration and to lightare obtained.

Instead of the compound (35), the compound (1) to (14), (16) to (20),(36) to (42), (93) to (98) and (118) to (130) can be employed with equalsuccess.

EXAMPLE 37

Commercially available polymethacrylate granules are mixed dry with 0.5percent by weight of the compound (36) and the mixture isinjection-moulded on a screw injection moulding machine at 220° C. Thetransparent mouldings which are coloured luminous yellow and have astrong yellow-green fluorescence possess very good fastness.

EXAMPLE 38

0.9 part of the compound (11) is mixed with 100 parts of finely dividedpolypropylene. The mixture is kneaded in an extruder at 210° to give ahomogeneously coloured mass which is extruded at 280°-300° through aspinneret plate. Fibers with a strong green-yellow fluorescence areobtained, the colouration of which is transparent, rub-resistant andvery fast to light.

We claim:
 1. Naphtholactam dyestuff of the formula ##STR122## wherein Y¹is hydrogen, C₁ -C₅ -alkyl, benzyl, C₁ -C₂ -alkylbenzyl, chlorobenzyl,C₁ -C₂ -alkoxybenzyl, cyanobenzyl, phenyl, C₁ -C₂ -alkylphenyl,chlorophenyl, C₁ -C₂ -alkoxyphenyl, cyclohexyl, or C₁ -C₅ -alkylsubstituted by chloro, hydroxy, cyano, carboxy, carboxylic acid C₁ -C₄-alkyl ester, benzyl ester, carboxylic acid amide, or C₁ -C₃ -alkoxy;Y²is hydrogen, chloro, bromo, C₁ -C₃ -alkyl, C₁ -C₁ -alkoxy, amino, orsulpho; Y¹ and Y², when taken together are trimethylene; Y³ is hydrogen,or C₁ -C₂ -alkoxy; and D is the remaining portion of acenaphtheneanthracene, benzindole, benz(dihydro) indole, phenanthrene, pyrene, orany of said rings substituted by 1-2 sulphonic acid groups. 2.Naphtholactam dyestuff of the formula ##STR123## wherein Z¹ is hydrogen,benzyl, C₁ -C₄ -alkyl, or C₁ -C₄ -alkyl substituted by hydroxy, chloro,or cyano;Z² is hydrogen, methyl, ethyl, or amino; and E is the remainingportion of an acenaphthene ring.
 3. Naphtholactam dyestuff of claim 1 ofthe formula ##STR124##
 4. Naphtholactam dyestuff of claim 1 of theformula ##STR125## wherein X is the number of 1 or
 2. 5. Naphtholactamdyestuff of claim 1 of the formula ##STR126##
 6. Naphtholactam dyestuffof claim 2 of the formula ##STR127##